Polyolefin and film comprising same

Abstract

The present invention relates to a polyolefin exhibiting excellent processability along with high stiffness and toughness characteristics, and a film comprising same.

Description

Polyolefin and film containing the same

[0001] Cross-citation with related applications

[0002] This application claims the benefit of priority to Korean Patent Application No. 10-2024-0087704, filed July 3, 2024, the entire contents of which are incorporated herein by reference.

[0003] The present invention relates to a polyolefin exhibiting excellent processability along with high stiffness and toughness characteristics, and a film comprising the same.

[0004]

[0005] Linear low-density polyethylene (LLDPE) is manufactured by copolymerizing ethylene and alpha olefin at low pressure using a polymerization catalyst. It is a resin with a narrow molecular weight distribution, short-chain branches of a certain length, and no long-chain branches. Linear low-density polyethylene film has the characteristics of general polyethylene, as well as high breaking strength and elongation, and excellent tear strength and drop impact strength, so it is increasingly being used in stretch films and overlap films, which are difficult to apply to conventional low-density polyethylene (LDPE) or high-density polyethylene (HDPE).

[0006] Recently, with the advent of decarbonization, demand for high-performance linear low-density polyethylene to improve recyclability is increasing, and along with this, demand for linear low-density polyethylene with excellent processability and drop impact strength is also increasing.

[0007] Dart drop impact strength is a crucial mechanical property that determines a resin's resistance to various impacts. However, despite its excellent mechanical properties, linear low-density polyethylene suffers from poor blown film processability and poor transparency. Blown film, also known as inflation film, is manufactured by blowing air into molten plastic to inflate it.

[0008] In addition, linear low-density polyethylene has excellent physical properties due to its uniform polymer structure, but has the disadvantage of poor processability due to its narrow molecular weight distribution. To compensate for this, a method using PPA (Polymer Processing Aid) containing fluorine compounds or introducing LCB (Long Chain Branch) was developed, but the density is 0.920 g / cm 3 In the above product group, it is difficult to find a product that simultaneously achieves excellent processability and excellent balance of physical properties, especially stiffness-toughness balance.

[0009] Accordingly, there is a need for the development of polyolefins that have excellent mechanical properties, processability and haze characteristics, and a balance of stiffness and toughness.

[0010]

[0011] In order to solve the problems of the above-mentioned prior art, the present invention aims to provide a polyolefin having a balanced stiffness-toughness property and excellent processability by optimizing the distribution of short chain branches (SCBs) and molecular weight distribution within a polymer structure without introducing long chain branches (LCBs).

[0012] In addition, the present invention seeks to provide a film comprising the polyolefin, specifically a blown film.

[0013]

[0014] According to the present invention,

[0015] A polyolefin is provided that satisfies the following conditions (1) to (3):

[0016] (1) Density measured by ASTM D1505 of 0.920 to 0.930 g / cm 3 ;

[0017] (2) In the temperature rising elution fractionation (TREF) graph during cross fraction chromatography (CFC) analysis, the toughness parameter (T1) expressed by Equation 1 satisfies T1>25;

[0018] [Formula 1]

[0019] T1 = 5*(W <76 * M <76 / 10 6 ) + (-1)*(W 76~88 * M 76~88 / 10 6 ) + (-2)*(W >88 * M >88 / 10 6 )

[0020] In the above equation 1,

[0021] W <76 , M <76 The weight ratio (wt%) and weight average molecular weight (g / mol) of the polymer fraction eluted below 76℃, respectively.

[0022] W 76~88 , M 76~88 The weight ratio (wt%) and weight average molecular weight (g / mol) of the polymer fraction eluted at 76℃ or higher and 88℃ or lower, respectively.

[0023] W >88 , M >88 Each represents the weight ratio (wt%) and weight average molecular weight (g / mol) of the polymer fraction eluted in the region exceeding 88℃,

[0024] (3) In the temperature rise elution fractionation (TREF) graph during cross-fraction chromatography (CFC) analysis, the Stiffness parameter (S1) expressed by Equation 2 satisfies S1>1.1;

[0025] [Formula 2]

[0026] S1 = W >88 / W ≥76 + W ≥76 / 100

[0027] In the above equation 2,

[0028] W >88 The weight ratio (wt%) of the polymer fraction eluted in the region exceeding 88℃,

[0029] W ≥76 , M ≥76 Each represents the weight ratio (wt%) and weight average molecular weight (g / mol) of the polymer fraction eluted in the region above 76℃.

[0030]

[0031] In addition, according to the present invention, a film including the polyolefin is provided.

[0032]

[0033] The polyolefin according to the present invention exhibits a balanced combination of rigidity and toughness properties, as well as excellent processability and transparency. Accordingly, it is useful for the production of films requiring high impact strength and excellent transparency, particularly blown films.

[0034]

[0035] Figure 1 is a TREF analysis graph for the polyolefin of Example 1.

[0036] Figure 2 is a TREF analysis graph for the polyolefin of Example 2.

[0037] Figure 3 is a TREF analysis graph for the polyolefin of Example 3.

[0038] Figure 4 is a TREF analysis graph for the polyolefin of Example 4.

[0039] Figure 5 is a TREF analysis graph for the polyolefin of Example 5.

[0040]

[0041] In the present invention, terms such as first, second, etc. are used to describe various components, and the terms are used only for the purpose of distinguishing one component from another.

[0042] Furthermore, the terminology used herein is merely for the purpose of describing exemplary embodiments and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly indicates otherwise. In this specification, it should be understood that the terms "comprise," "include," or "have" indicate the presence of a feature, number, step, component, or combination thereof, but do not preclude the possibility of the presence or addition of one or more other features, numbers, steps, components, or combinations thereof.

[0043] In the present invention, the weight ratio of a fraction or polymer eluted in any elution temperature range is calculated as a percentage (wt%) based on the total weight of all eluted fractions obtained through cross fraction chromatography (CFC) analysis.

[0044] In the present invention, the crystal structure characteristics of polyolefin can be determined through CFC analysis. The specific measurement method and conditions are as described in the experimental examples below.

[0045] The present invention is susceptible to various modifications and takes various forms. Specific embodiments are illustrated and described in detail below. However, this is not intended to limit the present invention to specific disclosed forms, but rather to encompass all modifications, equivalents, and alternatives falling within the spirit and technical scope of the present invention.

[0046]

[0047] Hereinafter, the polyolefin of the present invention and the film containing the same will be described in detail.

[0048]

[0049] The polyolefin according to the present invention satisfies the following conditions (1) to (3):

[0050] (1) Density measured by ASTM D1505 of 0.920 to 0.930 g / cm 3 ;

[0051] (2) In the temperature rising elution fractionation (TREF) graph during cross fraction chromatography (CFC) analysis, the toughness parameter (T1) expressed by Equation 1 satisfies T1>25;

[0052] [Formula 1]

[0053] T1 = 5*(W <76 * M <76 / 10 6 ) + (-1)*(W 76~88 * M 76~88 / 10 6 ) + (-2)*(W >88 * M >88 / 10 6 )

[0054] In the above equation 1,

[0055] W <76 , M <76The weight ratio (wt%) and weight average molecular weight (g / mol) of the polymer fraction eluted below 76℃, respectively.

[0056] W 76~88 , M 76~88 The weight ratio (wt%) and weight average molecular weight (g / mol) of the polymer fraction eluted at 76℃ or higher and 88℃ or lower, respectively.

[0057] W >88 , M >88 Each represents the weight ratio (wt%) and weight average molecular weight (g / mol) of the polymer fraction eluted in the region exceeding 88℃,

[0058] (3) In the temperature rise elution fractionation (TREF) graph during cross-fraction chromatography (CFC) analysis, the Stiffness parameter (S1) expressed by Equation 2 satisfies S1>1.1;

[0059] [Formula 2]

[0060] S1 = W >88 / W ≥76 + W ≥76 / 100

[0061] In the above equation 2,

[0062] W >88 The weight ratio (wt%) of the polymer fraction eluted in the region exceeding 88℃,

[0063] W ≥76 , M ≥76 Each represents the weight ratio (wt%) and weight average molecular weight (g / mol) of the polymer fraction eluted in the region above 76℃.

[0064]

[0065] Blown film extrusion, used in the production of packaging materials and various industrial films, is a method for mass-producing films with uniform thickness and surface area by expanding the film melted from a die through a screw by generating an air flow. It is mainly used to produce films with a relatively low melt index (MI), approximately 0.5 to 2.0. The process of expanding the polymer melt with air can impart uniform orientation in the mechanical direction (MD) and the transverse direction (TD) perpendicular to the stretching, thereby securing excellent mechanical properties.

[0066] However, due to the method of controlling bubble shape generation and cooling through air, transparency is inferior to that of cast film extrusion. Therefore, blending LDPE with LLDPE is primarily used to improve the film surface, but this method significantly reduces the film's mechanical properties.

[0067] Furthermore, while LLDPE possesses excellent physical properties due to its uniform polymer structure, its narrow molecular weight distribution hinders processability. To address this, a method using Polymer Processing Aid (PPA), which contains fluorinated compounds, has been used. However, with the recent expansion of regulations on the use of PPA, the need for improved processability is growing.

[0068] Instead of using PPA, products were released that improved processability by introducing LCB (Long Chain Branch) to LLDPE or adjusting the content and distribution of SCB (Short Chain Branch), but the density was 0.920 g / cm 3In the above product group, it is difficult to find a product that simultaneously achieves excellent processability and excellent balance of physical properties, especially stiffness-toughness balance.

[0069] Accordingly, there is a need for the development of polyolefins that have excellent mechanical properties, excellent processability without the introduction of LCB, and a balanced stiffness-toughness ratio, and for the quantification of their structure.

[0070]

[0071] Accordingly, in the present invention, the balance of stiffness and toughness properties of a polyolefin film was quantified and quantified through the polyolefin polymer structure, and T1 and S1 parameters were introduced.

[0072] First, the T1 parameter is a toughness factor expressed by Equation 1 below:

[0073] [Formula 1]

[0074] T1 = 5*(W <76 * M <76 / 10 6 ) + (-1)*(W 76~88 * M 76~88 / 10 6 ) + (-2)*(W >88 * M >88 / 10 6 )

[0075] In the above equation 1,

[0076] W <76 , M <76 The weight ratio (wt%) and weight average molecular weight (g / mol) of the polymer fraction eluted below 76℃, respectively.

[0077] W 76~88 , M 76~88 The weight ratio (wt%) of the polymer fraction eluted at 76℃ or higher and 88℃ or lower, respectively,

[0078] W >88 , M >88Each represents the weight ratio (wt%) and weight average molecular weight (g / mol) of the polymer fraction eluted in the region exceeding 88℃.

[0079] That is, in the above equation 1, W <76 , M <76 , W 76~88 , M 76~88 , W >88, and M >88 Each is a value calculated from the weight average molecular weight (g / mol) or percentage weight ratio (wt%) of crystal molecules eluted by temperature fraction in a temperature rising elution fractionation (TREF) graph during cross fraction chromatography (CFC) analysis of polyolefin.

[0080]

[0081] In each temperature fraction of the TREF graph, the polymer eluted in the relatively low temperature region (below 76℃) has a relatively high SCB content and when the molecular weight of the region is high, the polymer chains with a large distribution of SCB are likely to form tie molecules when forming a crystal structure, and the tie molecules have the effect of greatly improving the toughness in the polymer structure. Therefore, in Equation 1 (W <76 *M <76 / 100) If the value is high, more polymers are eluted in the region below 76℃, so it can be seen that high toughness is exhibited due to more tie-molecule formation.

[0082] Therefore, in equation 1 (W <76 * M <76 / 10 6 ) was set to 5 to have the highest weight and positive value.

[0083] On the other hand, in equation 1 (W 76~88 * M76~88 / 10 6 ) and (W >88 * M >88 / 10 6 ) refers to a polymer fraction with relatively little SCB, and when the content of the corresponding region is high and the molecular weight is high, tie-molecules are not formed and most of them form a crystal lattice structure (lamellar). This crystal structure is helpful for rigidity, but when a force with a high deformation rate is applied, it is difficult for the crystal structure to slip and deform due to the absence of SCB and tie-molecules, so it has the characteristic of becoming brittle. Therefore, this acts as a factor that hinders the rigidity of the entire polymer structure, so (W) eluted at an intermediate temperature 76~88 * M 76~88 / 10 6 ) The correlation coefficient of the part is -1, and (W) is dissolved at high temperature >88 *M >88 / 10 6 ) The correlation coefficient of the part was set with a weight of -2.

[0084]

[0085] Next, the S1 parameter is a stiffness factor expressed by Equation 2 below:

[0086] [Formula 2]

[0087] S1 = W >88 / W ≥76 + W ≥76 / 100

[0088] In the above equation 2,

[0089] W >88 The weight ratio (wt%) of the polymer fraction eluted in the region exceeding 88℃,

[0090] W ≥76 , M ≥76 Each represents the weight ratio (wt%) and weight average molecular weight (g / mol) of the polymer fraction eluted in the region above 76℃.

[0091] That is, in the above equation 2, W>88 , W ≥76 , and M ≥76 Each is a value calculated from the weight average molecular weight (g / mol) or percentage weight ratio (wt%) of crystal molecules eluted by temperature fraction in a temperature rising elution fractionation (TREF) graph during cross fraction chromatography (CFC) analysis of polyolefin.

[0092] W ≥76 , and W >88은 These represent the weight ratios of polymers eluted in the ranges of 76℃ or higher and 88℃ or higher, respectively, and the larger these ratios are, the more high-density polymers eluted at high temperatures are included. In general, the stiffness value is higher for polyolefins with higher density, and the more polymers eluted at high temperatures, the higher the density. Therefore, polyolefins with high S1 values ​​can exhibit high stiffness during polymer processing.

[0093]

[0094] In this way, the polyolefin according to one embodiment of the present invention has a density of 0.920 / cm 3 Compared to conventional polyolefins having a density above, it is possible to provide a polyolefin suitable for manufacturing a film having a balanced stiffness-toughness by having a high T1 value exceeding 25 and a T1 value exceeding 1.1.

[0095]

[0096] Accordingly, the polyolefin according to one embodiment of the present invention satisfies the conditions (1) to (3) below.

[0097] (1) Density measured by ASTM D1505 of 0.920 to 0.930 g / cm 3 ;

[0098] (2) In the temperature rising elution fractionation (TREF) graph during cross fraction chromatography (CFC) analysis, the toughness parameter (T1) expressed by Equation 1 satisfies T1>25;

[0099] [Formula 1]

[0100] T1 = 5*(W <76 * M <76 / 10 6 ) + (-1)*(W 76~88 * M 76~88 / 10 6 ) + (-2)*(W >88 * M >88 / 10 6 )

[0101] (3) In the temperature rise elution fractionation (TREF) graph during cross-fraction chromatography (CFC) analysis, the Stiffness parameter (S1) expressed by Equation 2 satisfies S1>1.1.

[0102] [Formula 2]

[0103] S1 = W >88 / W ≥76 + W ≥76 / 100

[0104]

[0105] Polyolefin according to one embodiment of the present invention has a viscosity of 0.920 to 0.930 g / cm when measured according to ASTM D1505. 3 It represents the density of . More specifically, 0.920 / cm 3 Ideal, or 0.921 / cm 3 Ideal, or 0.922 / cm 3 Ideal, or 0.923 / cm 3 Ideal, or 0.924 / cm 3 Ideal, or 0.925 / cm 3 Above, 0.930 / cm 3 or less, or 0.929 / cm3 or less, or 0.928 / cm 3 or less, or 0.927 / cm 3 or less, or 0.926 / cm 3 The density below is shown.

[0106] By exhibiting a density within the above range, excellent mechanical properties can be exhibited.

[0107]

[0108] According to one embodiment of the present invention, the polyolefin satisfies T1>25 in a temperature rising elution fractionation (TREF) graph during cross fraction chromatography (CFC) analysis, as represented by the above formula 1, in which the toughness parameter (T1) satisfies T1>25. More specifically, it may satisfy T1>25, or T1>26, or T1>27, or T1>28, or T1>29, or T1>30, while T1<45, or T1<44, or T1<43, or T1<42, or T1<41, or T1<40, or T1<39, or T1<38.

[0109] The description of T1 in the above formula 1 is as described above, and by satisfying T1 in the above range, the polyolefin according to the present invention can exhibit excellent toughness.

[0110]

[0111] According to one embodiment of the present invention, the polyolefin satisfies S1>1.1 in the temperature rising elution fractionation (TREF) graph in cross fraction chromatography (CFC) analysis, as represented by the above formula 2, in which the stiffness parameter (S1) satisfies S1>1.1. More specifically, S1>1.1, or S1>1.12, or S1>1.13, or S1>1.14, or S1>1.15, while S1<1.5, or S1<1.4, or S1<1.3, or S1<1.25, or S1<1.24, or S1<1.23, or S1<1.22.

[0112] The description of S1 in the above formula 2 is as described above, and by satisfying S1 within the above range, the polyolefin according to the present invention can exhibit excellent rigidity.

[0113]

[0114] According to one embodiment of the present invention, a polyolefin can satisfy P1>11 in a processing parameter (P1) expressed by the following equation 3 in a graph measured through cross-fraction chromatography (CFC).

[0115] [Formula 3]

[0116] P1 = 1.2 * Mw / Mn + 0.4 * Mz / Mn

[0117] In the above equation 3,

[0118] Mw represents the weight average molecular weight (g / mol) of polyolefin, Mn represents the number average molecular weight (g / mol), and Mz represents the Z average molecular weight (g / mol).

[0119]

[0120] The above P1 is a parameter representing processability, and the commonly used molecular weight distributions Mw / Mn (ratio of weight-average molecular weight to number-average molecular weight) and Mz / Mn (ratio of Z-average molecular weight to number-average molecular weight) were used as factors. First, the higher the Mw / Mn, the higher the content of the low-molecular region that receives less load during processing, showing characteristics that are advantageous for shear thinning, so the correlation coefficient was set to a value of 1.2. In the case of Mz / Mn, the influence of the Z-average molecular weight added to the specific gravity of the polymer region was also considered, and this can also reflect the processing characteristics by the broad molecular weight distribution, but considering the part that is offset by the polymer region, the correlation coefficient was set to a value of 0.4 to adjust the influence by the relevant region.

[0121] According to one embodiment of the present invention, the polyolefin satisfies the processing parameter (P1) represented by the above formula 3, P1>11. More specifically, it can satisfy P1>11, or P1>11.5, or P1>12, or P1>12.5, or P1>13, while P1<20, or P1<19, or P1<18, or P1<17, or P1<16, or P1<15.

[0122] By satisfying the above range of P1, the polyolefin according to the present invention can exhibit excellent processability.

[0123]

[0124] In addition, the polyolefin according to one embodiment of the present invention has a polymer structure expressed by the above parameters and MI 2.16 , MFRR(MI 21.6 / MI 2.16 ), it can exhibit excellent physical properties such as improved impact strength and transparency by further satisfying the optimal range conditions such as molecular weight distribution.

[0125] Specifically, the polyolefin according to one embodiment of the present invention has a melt index (MI) measured at a temperature of 190° C. and a load of 2.16 kg according to ASTM D1238. 2.16 ) may be 0.5 to 2 g / 10 min. More specifically, the melt index (MI 2.16 ) may be 0.5 g / 10 min or more, or 0.6 g / 10 min or more, or 0.7 g / 10 min or more, or 0.8 g / 10 min or more, or 0.9 g / 10 min or more, but 2.0 g / 10 min or less, 1.9 g / 10 min or less, 1.8 g / 10 min or less, 1.7 g / 10 min or less, or 1.6 g / 10 min or less, or 1.5 g / 10 min or less, or 1.4 g / 10 min or less, or 1.3 g / 10 min or less, or 1.2 g / 10 min or less.

[0126] In addition, the polyolefin according to one embodiment of the present invention has a melt index (MI) measured at a temperature of 190° C. and a load of 21.6 kg according to ASTM D1238 standard. 21.6 ) was measured at a temperature of 190 ℃ and a load of 2.16 kg. 2.16 ) is the MFRR (MI) ratio 21.6 / MI 2.16 ) can be 35 to 60 days. More specifically, MFRR (MI 21.6 / MI 2.16 ) may be 35 or more, or 36 or more, or 37 or more, or 38 or more, or 39 or more, or 40 or more, or 41 or more, or 42 or more, or 43 or more, or 44 or more, or 45 or more, but 60 or less, or 59 or less, or 58 or less, or 57 or less, or 56 or less, or 55 or less, or 54 or less, or 53 or less, or 52 or less, or 51 or less, or 50 or less.

[0127] In addition, the polyolefin according to one embodiment of the present invention exhibits a molecular weight distribution of 4.5 to 6. More specifically, it exhibits a molecular weight distribution of 4.5 or more, or 4.6 or more, or 4.7 or more, or 4.8 or more, or 4.9 or more, or 5.0 or more, and 6 or less, or 5.9 or less, or 5.8 or less, or 5.7 or less, or 5.6 or less, or 5.5 or less, or 5.4 or less, or 5.3 or less. By having a molecular weight distribution within the above range, it can exhibit excellent mechanical strength properties.

[0128]

[0129] The polyolefin according to one embodiment of the invention may specifically be a copolymer of ethylene and an alpha-olefin monomer.

[0130] Specific examples of the above alpha-olefin monomers include propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene, norbornene, norbornadiene, ethylidenenorbornene, phenylnorbornene, vinylnorbornene, dicyclopentadiene, 1,4-butadiene, 1,5-pentadiene, 1,6-hexadiene, styrene, alpha-methylstyrene, divinylbenzene, 3-chloromethylstyrene, etc., and two or more of these monomers may be mixed and copolymerized. More specifically, the alpha-olefin monomer may be 1-butene, 1-hexene, or 1-octene.

[0131]

[0132] The polyolefin according to the present invention having the above characteristics can be produced by a production method including a step of polymerizing an ethylene monomer and an alpha-olefin monomer while introducing hydrogen in the presence of a hybrid supported metallocene catalyst, which comprises, for example, a first transition metal compound represented by the following chemical formula 1; a second transition metal compound represented by the following chemical formula 2; a cocatalyst; and a carrier:

[0133] [Chemical Formula 1]

[0134]

[0135] In the above chemical formula 1,

[0136] M1 is a group 4 transition metal,

[0137] X 11 and X 12 are each independently, C 1-20 Alkyl, or halogen,

[0138] A1 is carbon, silicon, or germanium,

[0139] R 11 and R 12 are each independently, C 6-20 Aryl, C 7-20 Alkylaryl, C 7-20 Arylalkyl, or C 7-20 It is an alkoxyaryl,

[0140] Q 11 and Q 12 One of them is C 2-20 One is alkoxyalkyl, and the other is C 1-20 It is alkyl,

[0141] [Chemical Formula 2]

[0142]

[0143] In the above chemical formula 2,

[0144] M2 is a group 4 transition metal,

[0145] X 21 and X 22 are each independently, C 1-20 Alkyl or halogen,

[0146] R 21 Silver hydrogen, C 1-20 Alkyl, or C 2-20 It is an alkoxyalkyl,

[0147] R 22 Inland R 25 are each independently hydrogen, C 1-20 Alkyl, C 6-20 Aryl, C 7-20 Alkylaryl, or C7-20 Arylalkyl,

[0148] Q 21 and Q 22 are each independently, C 1-20 Alkyl or C 2-20 It is an alkoxyalkyl,

[0149] Q 21 and Q 22, and R 21 At least one of C 2-20 It is an alkoxyalkyl.

[0150]

[0151] In the present invention, the substituents of the chemical formula are described more specifically as follows.

[0152]

[0153] The halogen can be fluorine (F), chlorine (Cl), bromine (Br), or iodine (I).

[0154]

[0155] C above 1-20 The alkyl of may be straight-chain, branched-chain or cyclic alkyl. Specifically, the C 1-20 The alkyl may be a straight chain alkyl having 1 to 20 carbon atoms; a straight chain alkyl having 1 to 10 carbon atoms; a straight chain alkyl having 1 to 5 carbon atoms; a branched chain or cyclic alkyl having 3 to 20 carbon atoms; a branched chain or cyclic alkyl having 3 to 15 carbon atoms; or a branched chain or cyclic alkyl having 3 to 10 carbon atoms. More specifically, the alkyl having 1 to 20 carbon atoms may be a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, an n-pentyl group, an iso-pentyl group, or a cyclohexyl group.

[0156]

[0157] C 1-20 The alkoxy of may be a straight-chain, branched-chain or cyclic alkoxy group. Specifically, the C 1-20The alkoxy may be a straight chain alkoxy group having 1 to 20 carbon atoms; a straight chain alkoxy group having 1 to 10 carbon atoms; a straight chain alkoxy group having 1 to 5 carbon atoms; a branched chain or cyclic alkoxy group having 3 to 20 carbon atoms; a branched chain or cyclic alkoxy group having 3 to 15 carbon atoms; or a branched chain or cyclic alkoxy group having 3 to 10 carbon atoms. More specifically, the alkoxy group having 1 to 20 carbon atoms may be a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, an iso-butoxy group, a tert-butoxy group, an n-pentoxy group, an iso-pentoxy group, a neo-pentoxy group, or a cyclohexene group.

[0158]

[0159] C 2-20 Alkoxyalkyl of -R y -OR z Alkyl (-R) with a structure containing y ) is one or more hydrogens of alkoxy (-OR z ) may be a substituent substituted with. Specifically, the alkoxyalkyl having 2 to 20 carbon atoms may be a methoxymethyl group, a methoxyethyl group, an ethoxymethyl group, an iso-propoxymethyl group, an iso-propoxyethyl group, an iso-propoxyhectyl group, a tert-butoxymethyl group, a tert-butoxyethyl group, or a tert-butoxyhexyl group.

[0160] C 6-20 The aryl of may refer to a monocyclic, bicyclic or tricyclic aromatic hydrocarbon. Specifically, the C6 to C20 aryl may be a phenyl group, a naphthyl group or anthracenyl group.

[0161]

[0162] C 7-20 The alkylaryl of may mean a substituent in which one or more hydrogens of the aryl are replaced by alkyl. Specifically, the C 7-20The alkylaryl may be methylphenyl, ethylphenyl, n-propylphenyl, iso-propylphenyl, n-butylphenyl, iso-butylphenyl, tert-butylphenyl, di-tert-butylphenyl, or cyclohexylphenyl.

[0163]

[0164] C 7-20 Arylalkyl of may mean a substituent in which one or more hydrogens of alkyl are replaced by aryl. Specifically, the C 7-20 The arylalkyl group may be benzyl, phenylpropyl or phenylhexyl.

[0165]

[0166] C 7-20 Alkoxyaryl of -R c -OR d Aryl(-R) with a structure containing c ) is one or more hydrogens of alkoxy (-OR d ) may be a substituent substituted with. Specifically, the alkoxyaryl having 7 to 20 carbon atoms may be a methoxyphenyl group, an ethoxyphenyl group, an iso-propoxyphenyl group, or a tert-butoxyphenyl group.

[0167]

[0168] Also, group 4 transition metals can include titanium, zirconium, and hafnium.

[0169]

[0170] The hybrid supported metallocene catalyst according to the present invention is a hybrid catalyst comprising a first transition metal compound having a high molecular weight and high polymerizability, and a second transition metal compound having a low molecular weight and low polymerizability.

[0171]

[0172] Specifically, the first transition metal compound represented by the above chemical formula 1 contributes to producing a high molecular weight copolymer having a high SCB content, and the second transition metal compound represented by the above chemical formula 2 contributes to producing a low molecular weight copolymer having a low SCB (short chain branch) content.

[0173]

[0174] Accordingly, the hybrid supported metallocene catalyst of the present invention can exhibit high copolymerizability in polyolefins in the high molecular weight range due to the first transition metal compound, while exhibiting low copolymerizability in polyolefins in the low molecular weight range due to the action of the second transition metal compound. As a result, the polyolefin produced using the hybrid supported metallocene catalyst according to the present invention can exhibit a high MFRR compared to polyolefins having a similar density due to the introduction of LCB (long chain branch) in the high molecular weight range, and can exhibit excellent processability and high transparency.

[0175] In the hybrid supported metallocene catalyst according to the present invention, the first transition metal compound contributes to the production of a high molecular weight copolymer and exhibits a relatively high comonomer incorporation rate compared to the second transition metal compound.

[0176]

[0177] Specifically, in the above chemical formula 1, M1 is a Group 4 transition metal, preferably zirconium (Zr) or titanium (Ti), and more preferably zirconium (Zr).

[0178] X 11 and X 12 are each independently, C 1-20 Alkyl, or halogen, preferably halogen, more preferably chloro (Cl).

[0179] When Zr is included as the central metal of the first transition metal compound represented by the above chemical formula 1, compared to when other Group 14 elements such as Hf are included, it has more orbitals capable of accepting electrons, so it can easily bind to a monomer with higher affinity, and as a result, it can exhibit a superior catalytic activity improvement effect.

[0180]

[0181] In addition, the compound represented by the above chemical formula 1 is a bridge group of two indene derivative compounds, A1(Q 11 )(Q 12 ) includes a group. In the above chemical formula 1, A1 may be carbon, silicon, or germanium, and preferably silicon.

[0182] Q, a substituent of A1 11 and Q 12 One of them is C 2-20 One is alkoxyalkyl, and the other is C 1-20 Alkyl, preferably Q 11 and Q 12 One of them is C 1-4 One is alkyl, and the other is C 2-20 It may be an alkoxyalkyl. In this way, Q, which is a substituent of the above A1 11 and Q 12 Either one of C 2-20 It may contain a tether group of alkoxyalkyl. Q 11 and Q 12 If either of them has a tether group, leaching of the catalyst precursor is prevented during the polymerization reaction, and as a result, fouling caused by the reaction of the leached catalyst precursor and the cocatalyst can be prevented.

[0183] In addition, in addition to the leaching prevention effect of the above-mentioned catalyst precursor, compared to the carbon bridge in the conventional metallocene compound, the atomic size is larger and the available angle is increased, so that the monomer can easily approach during the polymerization reaction, thereby exhibiting better catalytic activity. This effect is achieved in the above-mentioned tether Q 11 and Q 12 Either one of -(CH2) n -R a (Above R a is C 1-6 Alkoxy group, more specifically C 1-6 Straight chain alkoxy group or C 3-6It may be a branched alkoxy group, more specifically a C such as a tert-butoxy group. 3-6 branched alkoxy, and n is an integer from 2 to 10, or from 3 to 9), and further, the remaining one is C 1-4 It can be further increased if it is alkyl. Preferably, Q 11 and Q 12 One of them may be tert-butoxypropyl, tert-butoxybutyl, tert-butoxypentyl, or tert-butoxyhexyl, and the other may be methyl.

[0184]

[0185] Also, in the above chemical formula 1, R 11 and R 12 are each independently, C 6-20 Aryl, C 7-20 Alkylaryl, C 7-20 Arylalkyl, or C 7-20 It is an alkoxyaryl. That is, in the chemical formula 1, the hydrogen at the 4th position of the indene derivative compound is each independently C 6-20 Aryl, C 7-20 Alkylaryl, C 7-20 Arylalkyl, or C 7-20 It can be substituted with an alkoxyaryl. As described above, when an indene derivative compound includes a substituent containing an aryl group, it can exhibit better catalytic activity due to the inductive effect that can supply sufficient electrons. Accordingly, the R 11 and R 12 is preferably C 6-20 Aryl, or C 7-20 It may be alkylaryl, more preferably phenyl, naphthyl, methylphenyl, ethylphenyl, n-propylphenyl, iso-propylphenyl, n-butylphenyl, iso-butylphenyl, tert-butylphenyl, di-tert-butylphenyl.

[0186] In addition, the methyl group substituted at position 2 of the indene derivative compound in chemical formula 1 can secure appropriate copolymerizability and molecular weight by the appropriate steric effect of ethylene and comonomer approaching the active site where polymerization proceeds.

[0187]

[0188] Specific examples of the first transition metal compound represented by the above chemical formula 1 include compounds having the following structures, but the present invention is not limited thereto.

[0189]

[0190]

[0191]

[0192]

[0193]

[0194] The first transition metal compound represented by the above chemical formula 1 can be synthesized by applying known reactions, and a more detailed synthesis method can be found in the examples.

[0195]

[0196] Meanwhile, the second transition metal compound represented by Chemical Formula 2 is a cross-linked structure of two cyclopentadiene derivative compounds, allowing for easy control of the electronic and steric environments surrounding the transition metal. As a result, the chemical structure, molecular weight distribution, and mechanical properties of the synthesized polyolefin can be easily controlled.

[0197]

[0198] Specifically, in the above chemical formula 2, M2 is a group 4 transition metal, preferably zirconium (Zr) or titanium (Ti), and more preferably zirconium (Zr).

[0199] X 21 and X 22are each independently, C 1-20 Alkyl, or halogen, preferably halogen, more preferably chloro (Cl).

[0200] When Zr is included as the central metal of the second transition metal compound represented by the above chemical formula 2, compared to when other Group 14 elements such as Hf are included, it has more orbitals capable of accepting electrons, so it can easily bind to a monomer with higher affinity, and as a result, it can exhibit a superior catalytic activity improvement effect.

[0201] In addition, the compound represented by the above chemical formula 2 is A2(Q) as a bridging group of two cyclopentadiene derivative compounds. 21 )(Q 22 ) includes a group. In the above chemical formula 2, A2 may be carbon, silicon, or germanium, and preferably silicon.

[0202]

[0203] In addition, in the second transition metal compound represented by the above chemical formula 2, R 22 Inland R 25 are each independently hydrogen, C 1-20 Alkyl, C 6-20 Aryl, C 7-20 Alkylaryl, or C 7-20 Arylalkyl, and Q 21 and Q 22 are each independently, C 1-20 Alkyl or C 2-20 It is an alkoxyalkyl, and the bridging group is A2(Q 21 )(Q 22 ) as a substituent Q 21 and Q 22 , and R, a substituent of a cyclopentadiene derivative compound 21 At least one of C 2-20 It is an alkoxyalkyl.

[0204] In this way, Q 21 and Q 22, and R 21 At least one of C 2-20 It may contain a tether group of alkoxyalkyl. Q 21 and Q 22 , and R 21 If at least one of the catalyst precursors has a tether group, leaching of the catalyst precursor is prevented during the polymerization reaction, and as a result, fouling caused by the reaction of the leached catalyst precursor and the cocatalyst can be prevented.

[0205] In addition, in addition to the leaching prevention effect of the above-mentioned catalyst precursor, compared to the carbon bridge in the conventional metallocene compound, the atomic size is larger and the available angle is increased, so that the monomer can easily approach during the polymerization reaction, thereby exhibiting better catalytic activity. This effect is the Q 21 and Q 22 , and R 21 At least one of -(CH2) n -R b (Above R b is C 1-6 Alkoxy group, more specifically C 1-6 Straight chain alkoxy group or C 3-6 It may be a branched alkoxy group, more specifically a C such as a tert-butoxy group. 3-6 branched alkoxy, and n is an integer from 2 to 10, or from 3 to 9), and further, the remaining one is C 1-4 It can be further increased if it is alkyl. Preferably, Q 21 and Q 22 , and R 21 Any one or more of them may be tert-butoxyethyl, tert-butoxypropyl, tert-butoxybutyl, tert-butoxypentyl, or tert-butoxyhexyl.

[0206]

[0207] In addition, in the second transition metal compound represented by the above chemical formula 2, R 22 Inland R 25 are each independently hydrogen, C 1-20 Alkyl, C 6-20 Aryl, C 7-20 Alkylaryl, or C 7-20 It is arylalkyl. R 22 Inland R 25 are preferably each independently hydrogen, C 1-6 Alkyl, or C 6-10 It can be aryl, and more preferably, hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, phenyl, naphthyl, methylphenyl, ethylphenyl, n-propylphenyl, iso-propylphenyl, n-butylphenyl, iso-butylphenyl, tert-butylphenyl, di-tert-butylphenyl.

[0208] In the above chemical formula 2, one of the cyclopentadiene derivative compounds is R 22 Inland R 25 By substituting with a substituent of the first transition metal compound represented by the above chemical formula 1, it can exhibit superior catalytic activity due to the inductive effect that can supply sufficient electrons and the appropriate steric effect, and by appropriately controlling the distribution of the comonomer of the polyolefin manufactured in combination with the first transition metal compound represented by the above chemical formula 1, it can simultaneously improve dosability and processability. In addition, it exhibits excellent hydrogen reactivity, so that the amount of wax generated during the polymerization reaction can be reduced, and as a result, process stability can be improved.

[0209]

[0210] Specific examples of the second transition metal compound represented by the above chemical formula 2 include compounds having the following structures, but the present invention is not limited thereto.

[0211] ​

[0212]

[0213] .

[0214]

[0215] The second transition metal compound represented by the above chemical formula 2 can be synthesized by applying known reactions, and a more detailed synthesis method can be found in the examples.

[0216]

[0217] Meanwhile, the hybrid supported metallocene catalyst according to the present invention can increase catalytic activity and further improve the properties of the polymer produced by controlling the molar ratio of the first and second transition metal compounds.

[0218]

[0219] For example, the hybrid supported metallocene catalyst may include the first and second transition metal compounds in a molar ratio of 1:10 to 10:1. When the above-mentioned mixing ratio condition is satisfied, the activity of the catalyst is excellently maintained, and the high and low copolymerizabilities of the polyolefin produced from the hybrid supported catalyst are optimized, thereby further improving transparency and processability. More specifically, the molar ratio of the first and second transition metal compounds may be 1:10 or more, or 1:5 or more, or 1:4 or more, or 1:3 or more, or 1:2 or more, or 1:1 or more, and 10:1 or less, or 5:1 or less, or 4:1 or less, or 3:1 or less, or 2:1 or less.

[0220]

[0221] In addition, the hybrid supported metallocene catalyst according to the present invention includes a cocatalyst. When the hybrid supported metallocene catalyst includes a cocatalyst, it can exhibit high catalytic activity while improving process stability.

[0222] Specifically, the cocatalyst may include at least one compound represented by the following chemical formula 3.

[0223] [Chemical Formula 3]

[0224] -[Al(R 41 )-O]a-

[0225] In the above chemical formula 3,

[0226] R 41 is a halogen; or C substituted or unsubstituted with a halogen 1-20 It is hydrocarbyl;

[0227] a is an integer greater than or equal to 2.

[0228]

[0229] Meanwhile, in the present specification, a hydrocarbyl group is a monovalent functional group in the form of removing a hydrogen atom from a hydrocarbon, and may include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, an aralkenyl group, an aralkynyl group, an alkylaryl group, an alkenylaryl group, and an alkynylaryl group. In addition, the hydrocarbyl group having 1 to 20 carbon atoms may be a hydrocarbyl group having 1 to 15 carbon atoms or 1 to 10 carbon atoms. Specifically, the hydrocarbyl group having 1 to 20 carbon atoms is a straight-chain, branched-chain, or cyclic alkyl group such as a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, or a cyclohexyl group; Or it may be an aryl group such as a phenyl group, a naphthyl group, or anthracenyl group.

[0230]

[0231] Examples of compounds represented by the above chemical formula 3 include alkylaluminoxane compounds such as methylaluminoxane, ethylaluminoxane, isobutylaluminoxane, or butylaluminoxane, and any one of these or a mixture of two or more thereof may be used.

[0232]

[0233] Among the above compounds, the cocatalyst may be, more specifically, an alkylaluminoxane cocatalyst such as methylaluminoxane.

[0234]

[0235] The above alkylaluminoxane cocatalyst can further enhance catalytic activity by including a metal element that stabilizes the first and second transition metal compounds and acts as a Lewis acid to form a bond through a Lewis acid-base interaction with a functional group introduced into a bridge group of the first and second transition metal compounds.

[0236]

[0237] In addition, the amount of the cocatalyst used can be appropriately adjusted depending on the properties or effects of the desired catalyst and polyolefin. For example, when silica is used as the carrier described below, the cocatalyst can be supported in an amount of 100 g or more, or 1000 g or more, or 2000 g or more, and 6000 g or less, or 5500 g or less, or 5400 g or less, based on the weight of the carrier, for example, 1,000 g of silica.

[0238]

[0239] In addition, the hybrid supported metallocene catalyst according to the present invention may include a carrier. When the hybrid supported metallocene catalyst includes a carrier, the first and second transition metal compounds are used in the form of a supported catalyst supported on the carrier.

[0240]

[0241] As the carrier, a carrier having a highly reactive hydroxyl group, silanol group, or siloxane group on the surface can be used, and for this purpose, a carrier whose surface has been modified by calcination or whose surface has had moisture removed by drying can be used.

[0242]

[0243] For example, silica manufactured by calcining silica gel, silica such as silica dried at high temperature, silica-alumina, and silica-magnesia can be used, and these can typically contain oxide, carbonate, sulfate, and nitrate components such as Na2O, K2CO3, BaSO4, and Mg(NO3)2.

[0244]

[0245] When used in a supported catalyst state, the particle shape and bulk density of the polymer produced are excellent, and it can be suitably used in conventional slurry polymerization, bulk polymerization, and gas phase polymerization processes. In addition, among various supports, the silica support is supported by chemical bonding of the functional group of the transition metal compound, so that almost no catalyst is liberated from the support surface during the ethylene polymerization process, and as a result, when producing polyolefin by slurry or gas phase polymerization, fouling caused by adhesion of the reactor wall or polymer particles to each other can be minimized.

[0246]

[0247] The above-mentioned carrier may have an average particle diameter (D50) of 20 to 40 μm. When the above-mentioned particle size is present, the transition metal compound can be supported with superior efficiency, and as a result, the catalytic activity can be enhanced. More specifically, the carrier may have an average particle diameter of 20 μm or more, or 25 μm or more, and 40 μm or less, or 30 μm or less.

[0248]

[0249] In addition, when supported on the carrier, the first and second transition metal compounds may be supported in an amount of, for example, 1 mmol or more, 3 mmol or more, 5 mmol or more, 7 mmol or more, or 10 mmol or more, and 100 mmol or less, or 80 mmol or less, or 60 mmol or less, or 50 mmol or less, based on 1,000 g of the silica carrier. When supported in the above amount range, it may exhibit appropriate supported catalytic activity, which may be advantageous in terms of maintaining the activity of the catalyst and economic efficiency.

[0250]

[0251] The hybrid supported metallocene catalyst according to the present invention having the above-described configuration can be produced by a manufacturing method including a step of supporting a promoter compound on a support, and a step of supporting the first and second transition metal compounds on the support, wherein the supporting order of the promoter and the first and second transition metal compounds can be changed as needed, and the supporting order of the first and second transition metal compounds can also be changed as needed. The first and second transition metal compounds may be supported simultaneously. Considering the effect of the supported catalyst having a structure determined according to the supporting order, among these, supporting the promoter on the support and then sequentially supporting the first and second transition metal compounds can enable the produced supported catalyst to realize high catalytic activity and better process stability in the process of producing a polyolefin.

[0252]

[0253] The above polymerization reaction is carried out under the condition of hydrogen input.

[0254] Specifically, hydrogen may be introduced in an amount of 5 to 500 ppm, more specifically 5 ppm or more, or 10 ppm or more, or 20 ppm or more, or 30 ppm or more, and 500 ppm or less, or 450 ppm or less, or 400 ppm or less, or 350 ppm or less, or 300 ppm or less, or 250 ppm or less, or 200 ppm or less, based on the total weight of monomers including ethylene monomers and alpha-olefin monomers. When introduced in the above range, it may be easier to implement the properties of the above-mentioned polyolefin. When the polymerization reaction is performed under conditions without introducing hydrogen, the melt index (MI) of the polyolefin produced may be significantly reduced.

[0255]

[0256] The amount of the alpha-olefin monomer added may be determined depending on the properties of the polyolefin to be manufactured. For example, considering the effects of improving the properties, transparency, and processability of the polyolefin to be implemented in the present invention, the alpha-olefin monomer may be added in an amount of 5 to 20 wt% based on the total weight of monomers including ethylene monomers and alpha-olefin monomers. More specifically, the alpha-olefin monomer may be added in an amount of 5 wt% or more, or 6 wt% or more, or 7 wt% or more, or 8 wt% or more, or 9 wt% or more, or 10 wt% or more, and 20 wt% or less, or 19 wt% or less, or 18 wt% or less, or 17 wt% or less, based on the total weight of monomers including ethylene monomers and alpha-olefin monomers.

[0257] The above polymerization reaction can be carried out as a slurry polymerization reaction.

[0258] Accordingly, it can be performed using a single continuous slurry polymerization reactor or a loop slurry reactor.

[0259] In addition, the hybrid supported catalyst can be dissolved or diluted and injected into an aliphatic hydrocarbon solvent having 4 to 12 carbon atoms, such as isobutane, pentane, hexane, heptane, nonane, decane, and their isomers, an aromatic hydrocarbon solvent such as toluene and benzene, a hydrocarbon solvent substituted with a chlorine atom such as dichloromethane and chlorobenzene, etc. It is preferable to use the solvent used here after removing a small amount of water or air, etc. that act as catalyst poisons, by treating it with a small amount of alkyl aluminum, and it is also possible to use it by further using a cocatalyst.

[0260]

[0261] In addition, the polymerization reaction may be carried out at a temperature of 40°C or higher, or 60°C or higher, or 80°C or higher, and 110°C or lower, or 100°C or lower, or 90°C or lower. In addition, when the pressure conditions during the polymerization reaction are further controlled, the polymerization reaction may be carried out under a pressure of 5 bar or higher, or 10 bar or higher, or 20 bar or higher, and 50 bar or lower, or 45 bar or lower, or 40 bar or lower. When the polymerization proceeds under such temperature and pressure, the desired properties of the polyolefin can be more easily realized.

[0262]

[0263] The polyolefin manufactured using the above-described manufacturing method exhibits excellent processability, represented by processing pressure, and transparency, measured by haze. In a preferred embodiment, the polyolefin may be an ethylene / 1-hexene copolymer.

[0264]

[0265] Hereinafter, preferred examples are presented to aid understanding of the present invention. However, the following examples are provided solely to facilitate understanding of the present invention and are not intended to limit the scope of the present invention.

[0266]

[0267] <Example>

[0268] <Preparation of Transition Metal Compounds>

[0269] Synthesis Example 1-1

[0270] (Cat 1-1)

[0271]

[0272] Preparation of ligand compounds

[0273] 6-Chlorohexan-1-ol (1 equiv.) was dissolved in hexane (1 M), and Amberlyst (10 wt%) was added. Isobutene gas was bubbled at room temperature for 3 hours. 1-(tert-butoxy)-6-chlorohexane was obtained by filtering through Celite and vacuum drying. Mg (1.5 eq) was prepared in another flask, washed with HCl and acetone, and vacuum dried. THF (1 M) was added, and 10% 1-(tert-butoxy)-6-chlorohexane was added. After refluxing and completing activation, the mixture was cooled to 50°C, and the remaining 90% 1-(tert-butoxy)-6-chlorohexane was slowly added. The reaction was maintained overnight. The mixture was filtered through Celite, and 1 equivalent of MeSiCl3 was dissolved in THF (1 M) in a new flask, and Grignard reagent was slowly added at -25°C. The mixture was stirred overnight at room temperature, the solvent was completely dried, and the mixture was filtered after replacing with hexane to obtain (6-(tert-butoxy)hexyl)dichloro(methyl)silane.

[0274] 2-Methyl-7-phenyl-1H-indene (16.00 mmol) was added to a Schlink flask and dried under reduced pressure for 30 minutes. THF (60 mL) was added and stirred to completely dissolve. After cooling the flask to -25 °C, n-BuLi (2.5 M, 6.4 mL) was slowly added dropwise with stirring. After stirring at 25 °C for 12 hours, CuCN (5 mol%) was added. After stirring for 30 minutes, it was cooled to -25 °C. (6-(tert-butoxy)hexyl)dichloro(methyl)silane (8.00 mmol) was added and stirred at 25 °C for 12 hours. Water was added, stirred for 1 hour, and then extracted. The organic layer was dehydrated with MgSO4, filtered, and dried again to obtain the ligand compound.

[0275]

[0276] Preparation of transition metal compounds

[0277] To the ligand compound obtained above, 21 mL of toluene and 2.1 mL of diethyl ether were added and stirred. After cooling to -25 °C, n-BuLi (2.5 M, 12.8 mL) was slowly added dropwise while stirring. The mixture was stirred at 25 °C for 12 h and cooled to -20 °C, and then ZrCl4·2THF (8.00 mmol) dissolved in toluene (1 M) was added. After stirring at 25 °C for 12 h, the solvent was completely dried. The mixture was dissolved in DCM, filtered, and the filtrate was dried and recrystallized using dichloromethane, pentane, and hexane to obtain a transition metal compound of structural formula Cat 1-1 in a yield of 35% (racemic / meso ratio of 30:1).

[0278]

[0279] 1H NMR (500 MHz, C6D6, 7.15 ppm): 1.19(9H, s), 1.32(3H, s), 1.48~1.86(10H, m), 2.25(6H, s), 3.37(2H, t), 6.95(2H, s), 7.13(2H, t), 7.36(2H, d), 7.43(6H, t), 7.62(4H, d), 7.67(2H, d)

[0280]

[0281] Synthesis Example 1-2

[0282] (Cat 1-2)

[0283]

[0284]

[0285] Preparation of ligand compounds

[0286] A ligand compound was prepared in the same manner as the preparation of the ligand compound of Synthesis Example 1-1, except that 4-chlorobutan-1-ol was used instead of 6-chlorohexan-1-ol in Synthesis Example 1-1.

[0287]

[0288] Preparation of transition metal compounds

[0289] Except that the ligand compound of Synthesis Example 1-2 was used instead of the ligand compound of Synthesis Example 1-1, the same method as for preparing the transition metal compound of Synthesis Example 1-1 was used, and the transition metal compound of structural formula Cat 1-2 was obtained in a yield of 40% (ratio of racemic / meso 20:1).

[0290]

[0291] 1 H NMR (500 MHz, C6D6, 7.15 ppm): 1.21(9H, s), 1.33(3H, s), 1.58~1.96(6H, m), 2.31(6H, s), 3.42(2H, t), 6.98(2H, s), 7.15(2H, t), 7.38(2H, d), 7.45-7.54(10H, m), 7.28(2H, d)

[0292]

[0293] Synthesis Example 1-3

[0294] (Cat 1-3)

[0295]

[0296]

[0297] Preparation of ligand compounds

[0298] A ligand compound was prepared in the same manner as the preparation of the ligand compound of Synthesis Example 1-1, except that 1-(2-methyl-1H-inden-7-yl)naphthalene was used instead of 2-methyl-7-phenyl-1H-indene in Synthesis Example 1-1.

[0299]

[0300] Preparation of transition metal compounds

[0301] Except that the ligand compound of Synthesis Example 1-3 was used instead of the ligand compound of Synthesis Example 1-1, the same method as for preparing the transition metal compound of Synthesis Example 1-1 was used, and the transition metal compound of structural formula Cat 1-3 was obtained in a yield of 25% (ratio of racemic / meso 15:1).

[0302]

[0303] 1 H NMR (500 MHz, CDCl3, 7.26 ppm): 0.80~2.15 (31H, m), 2.23 (6H, d), 3.43 (2H, t), 6.57 (2H, s), 6.95~8.00 (20H, m)

[0304]

[0305] Synthesis Example 1-4

[0306] (Cat 1-4)

[0307]

[0308]

[0309] Preparation of ligand compounds

[0310] A ligand compound was prepared in the same manner as the preparation of the ligand compound of Synthesis Example 1-1, except that 7-(4-(tert-butyl)phenyl)-2-methyl-1H-indene was used instead of 2-methyl-7-phenyl-1H-indene in Synthesis Example 1-1.

[0311]

[0312] Preparation of transition metal compounds

[0313] Except that the ligand compound of Synthesis Example 1-4 was used instead of the ligand compound of Synthesis Example 1-1, the same method as for preparing the transition metal compound of Synthesis Example 1-1 was used, and the transition metal compound of structural formula Cat 1-4 was obtained in a yield of 34% (ratio of racemic / meso 30:1).

[0314]

[0315] 1 H NMR (500 MHz, CDCl3, 7.26 ppm): 1.20 (9H, s), 1.27 (3H, s), 1.34 (18H, s), 1.20-1.90 (10H, m), 2.25 (3H, s), 2.26 (3H, s), 3.38 (2H, t), 7.00 (2H, s), 7.09-7.13 (2H, m), 7.38 (2H, d), 7.45 (4H, d), 7.58 (4H, d), 7.59 (2H, d), 7.65 (2H, d)

[0316]

[0317] Synthesis Example 2-1

[0318] (Cat 2-1)

[0319]

[0320]

[0321] Preparation of ligand compounds

[0322] 6-Chlorohexan-1-ol (1 equiv) was dissolved in hexane (1 M), and Amberlyst (10 wt%) was added. Isobutene gas was bubbled at room temperature for 3 hours. 1-(tert-butoxy)-6-chlorohexane was obtained by filtering through celite and drying in vacuum. 1-(tert-butoxy)-6-chlorohexane (20.0 mmol) was weighed into a flask, and THF (1.0 M) was added. After cooling to -25 °C, sodium cyclopentadiene (1.0 M in THF, 1 eq) was added. After stirring at room temperature for 12 hours, the solvent was completely dried, hexane was replaced, and filtering was performed to obtain 1-(6-(tert-butoxy)hexyl)cyclopenta-1,3-diene.

[0323] Tetramethylcyclopentadiene (10.00 mmol) was added to a Schlenk flask and dried under reduced pressure for 30 minutes. THF (40 mL) was added, cooled to -25 °C, and n-BuLi (2.5 M, 4 mL) was slowly added dropwise with stirring. The mixture was stirred at 25 °C for 12 hours and then cooled to -25 °C. Me2SiCl2 (dichlorodimethylsilane, 10.00 mmol) was added and stirred at 25 °C for 12 hours. In another flask, previously synthesized 1-(6-(tert-butoxy)hexyl)cyclopenta-1,3-diene (10.00 mmol) and THF (40 mL) were added, cooled to -25 °C, and n-BuLi (2.5 M, 4 mL) was slowly added dropwise with stirring. The mixture was then stirred at 25 °C for 12 hours. After cooling the previously synthesized Chlorodimethyl(2,3,4,5-tetramethylcyclopenta-2,4-dien-1-yl)silane flask to -25 ℃, Lithium 1-(6-(tert-butoxy)hexyl)cyclopenta-1,3-diene was slowly added dropwise. After stirring at 25 ℃ for 12 hours, water was added, stirring for 1 hour, and extraction was performed. The organic layer was dehydrated with MgSO4, filtered again, and dried to obtain the ligand compound.

[0324]

[0325] Preparation of transition metal compounds

[0326] 25 mL of diethyl ether was added to the ligand compound obtained above and stirred. After cooling to -25 °C, n-BuLi (2.5 M, 8 mL) was slowly added dropwise while stirring. The mixture was stirred at 25 °C for 12 h and cooled to -20 °C, and then ZrCl4·2THF (10.00 mmol) dissolved in toluene (1 M) was added. After stirring at 25 °C for 12 h, the solvent was completely dried. DCM was added, filtered, the filtrate was dried, and recrystallized using hexane to obtain a transition metal compound of structural formula Cat 2-1 in a yield of 25%.

[0327]

[0328] 1 H NMR (500 MHz, C6D6, 7.15 ppm): 0.37(3H, s), 0.39(3H, s), 1.12(9H, s), 1.32-1.40(4H, m), 1.53-1.60(4H, m), 1.66(3H, s), 1.73(3H, s), 2.01(3H, s), 2.03(3H, s), 2.79-2.85(2H, m), 3.23(2H, t), 5.16(1H, t), 5.43(1H, t), 6.73(1H, t)

[0329]

[0330] Synthesis Example 2-2

[0331] (Cat 2-2)

[0332]

[0333]

[0334] Preparation of ligand compounds

[0335] A ligand compound was prepared in the same manner as the preparation of the ligand compound of Synthesis Example 2-1, except that 4-chlorobutan-1-ol was used instead of 6-chlorohexan-1-ol in Synthesis Example 2-1.

[0336]

[0337] Preparation of transition metal compounds

[0338] Except that the ligand compound of Synthesis Example 2-2 was used instead of the ligand compound of Synthesis Example 2-1, the preparation was carried out in the same manner as the preparation of the transition metal compound of Synthesis Example 2-1, and a transition metal compound of structural formula Cat 2-2 was obtained in a yield of 40%.

[0339]

[0340] 1 H NMR (500 MHz, C6D6, 7.15 ppm): 0.39(3H, s), 0.40(3H, s), 1.14(9H, s), 1.42-1.50(4H, m), 1.68(3H, s), 1.75(3H, s), 2.05(3H, s), 2.07(3H, s), 2.85-2.92(2H, m), 3.25(2H, t), 5.18(1H, t), 5.44(1H, t), 6.75(1H, t)

[0341]

[0342] Synthesis Example 2-5

[0343] (Cat 2-5)

[0344]

[0345]

[0346] Preparation of ligand compounds

[0347] A ligand compound was prepared in the same manner as the preparation of the ligand compound in Synthesis Example 2-1, except that (3,5-dimethylcyclopenta-2,5-diene-1,2-diyl)dibenzene was used instead of Tetramethylcyclopentadiene in Synthesis Example 2-1.

[0348]

[0349] Preparation of transition metal compounds

[0350] Except that the ligand compound of Synthesis Example 2-5 was used instead of the ligand compound of Synthesis Example 2-1, the preparation was carried out in the same manner as the preparation of the transition metal compound of Synthesis Example 2-1, and the transition metal compound of structural formula Cat 2-5 was obtained in a yield of 54%.

[0351]

[0352] 1 H NMR (500 MHz, C6D6, 7.15 ppm): 0.32(3H, s), 0.33(3H, s), 1.14(9H, s), 1.36-1.46(4H, m), 1.51-1.62(4H, m), 2.90-2.92(2H, m), 3.44(2H, t), 5.18(1H, t), 5.45(1H, t), 5.48(2H, s), 6.72(1H, t), 7.09-7.18(10H, m)

[0353]

[0354] Synthesis Example 2-6

[0355] (Cat 2-6)

[0356]

[0357]

[0358] Preparation of ligand compounds

[0359] Tetramethylcyclopentadiene (10.00 mmol) was added to a Schlenk flask and dried under reduced pressure for 30 minutes. THF (40 mL) was added, cooled to -25 °C, and n-BuLi (2.5 M, 4 mL) was slowly added dropwise with stirring. The mixture was stirred at 25 °C for 12 hours and then cooled to -25 °C. (6-(tert-butoxy)hexyl)dichloro(methyl)silane (10.00 mmol) prepared in Synthesis Example 1-1 was added and stirred at 25 °C for 12 hours. After cooling to -25 °C, NaCp (1.0 M in THF, 1 eq) was slowly added dropwise. After stirring at 25 °C for 12 hours, water was added, stirred for 1 hour, and then extracted. The organic layer was dehydrated with MgSO4, filtered, and dried again to obtain the ligand compound.

[0360]

[0361] Preparation of transition metal compounds

[0362] 25 mL of diethyl ether was added to the ligand compound obtained above and stirred. After cooling to -25 °C, n-BuLi (2.5 M, 8 mL) was slowly added dropwise while stirring. The mixture was stirred at 25 °C for 12 h and cooled to -20 °C, and then ZrCl4·2THF (10.00 mmol) dissolved in toluene (1 M) was added. After stirring at 25 °C for 12 h, the solvent was completely dried. DCM was added, filtered, the filtrate was dried, and recrystallized using hexane to obtain a transition metal compound of structural formula Cat 2-6 in a yield of 32%.

[0363]

[0364] 1H NMR (500 MHz, CDCl3, 7.26 ppm): 0.82(3H, s), 1.18(9H, s), 1.24-1.66(10H, m), 1.92(3H, s), 1.94(3H, s), 2.03(6H, s), 3.33(2H, s), 5.69(2H, dd), 7.00(2H, dd)

[0365]

[0366] Synthesis Example 3-9

[0367] (Cat 3-9)

[0368]

[0369] A transition metal compound of the structural formula Cat 3-9 was prepared using the same method as Synthesis Example 4 of Korean Patent Publication No. 2017-0073463.

[0370]

[0371] Synthesis Example 3-11

[0372] (Cat 3-11)

[0373]

[0374] A transition metal compound of the structural formula Cat 3-11 was prepared using the same method as Synthesis Example 6 of Korean Patent Publication No. 2017-0073463.

[0375]

[0376] <Preparation of Hybrid Supported Metallocene Catalysts>

[0377] Manufacturing Example 1

[0378] 2.0 kg of toluene and 1000 g of silica (Grace Davison, SP2410) were charged into a 20L SUS high-pressure reactor, and stirred while raising the temperature of the reactor to 40°C. 5.4 kg of methylaluminoxane (10 wt% in toluene, manufactured by Albemarle) was charged into the reactor, and the temperature was raised to 70°C, followed by stirring at about 200 rpm for about 12 hours. Thereafter, the temperature of the reactor was lowered to 40°C, and stirring was stopped. The reaction product was allowed to stand for about 10 minutes and then decantated. 2.0 kg of toluene was then added to the reaction product, stirred for about 10 minutes, stopped, allowed to stand for about 30 minutes, and then decantated.

[0379] 2.0 kg of toluene was charged into the reactor, and then the first transition metal compound of structural formula Cat 1-1 (40.0 mmol) prepared in Synthesis Example 1-1, the second transition metal compound of structural formula Cat 2-2 (20.0 mmol) prepared in Synthesis Example 2-2, and 1000 mL of toluene were charged. The temperature of the reactor was raised to 85°C, and stirring was performed for approximately 90 minutes.

[0380] Afterwards, the temperature of the reactor was lowered to room temperature, stirring was stopped, the reaction product was allowed to stand for about 30 minutes, and the reaction product was decantated. Next, 3 kg of hexane was added to the reactor, and the hexane slurry solution was transferred to a 20 L filter dryer, the solution was filtered, and dried under reduced pressure at 50 °C for about 4 hours to obtain about 1.5 kg of a hybrid supported metallocene catalyst.

[0381]

[0382] Manufacturing Examples 2 to 5 and Comparative Manufacturing Examples 1 to 2

[0383] As described in Table 1 below, a hybrid supported metallocene catalyst was prepared in the same manner as in Preparation Example 1, except that the types of the first and second transition metal compounds were changed.

[0384]

[0385] Catalyst1 Transition metal compound2 Transition metal compoundPreparation example 1 Cat 1-1 Cat 2-2Preparation example 2 Cat 1-1 Cat 2-5Preparation example 3 Cat 1-1 Cat 2-6Preparation example 4 Cat 1-2 Cat 2-1Preparation example 5 Cat 1-3 Cat 2-1Comparative preparation example 1 Cat 1-4 Cat 3-9Comparative preparation example 2 Cat 1-4 Cat 3-11

[0386] <Production of polyolefin> Examples 1 to 5 and Comparative Examples 1 to 2

[0387] A 140 L continuous polymerizer capable of performing an isobutene slurry loop process with a polymerization reactor and operating at a reaction velocity of approximately 7 m / s was prepared. The reactants required for polyolefin polymerization were continuously fed into the reactor as described in Tables 2 and 3. The catalysts used in each polymerization reaction were those prepared in the manufacturing examples or comparative manufacturing examples described in Table 1, and were mixed with the isobutene slurry and fed. The polymerization reaction was performed at a pressure of approximately 40 bar and a temperature of approximately 85°C.

[0388] The main conditions of the above polymerization reaction are shown in Table 2.

[0389]

[0390] Comparative Example 3

[0391] M2710HN (manufactured by Hanwha Solutions) was commercially obtained and used.

[0392]

[0393] Comparative Example 4

[0394] XM3108BN (manufactured by LG Chemical) was obtained commercially and used.

[0395]

[0396] Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Catalyst Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Preparation Example 5 Comparative Preparation Example 1 Comparative Preparation Example 2 Ethylene input (kg / hr) 25 20.3 19.8 19.3 2122 19 1 - Hexene input (wt%) 14.0 14.0 14.8 14.0 14.4 13.4 11.0 Hydrogen input (ppm) 110 135 135 28 165 70 64 Activity (kgPE / kgSiO2·hr) 7.6 3.9 4.11 1.5 2.12.6

[0397] In the above Table 2, the activity (Activity, kgPE / kgSiO2·hr) was calculated as the ratio of the weight of polymer (kg PE) produced per weight of supported catalyst (kg) used per unit time (hr). In addition, the 1-Hexene input amount (wt%) was calculated as a percentage of the 1-Hexene input amount based on the total weight of monomers including ethylene and 1-hexene, and the hydrogen input amount (ppm) was calculated as a percentage of the total weight of monomers including ethylene and 1-hexene.

[0398]

[0399] <Experimental Example>

[0400] Evaluation of physical properties of polyolefins

[0401] The physical properties of the polyolefins of the examples and comparative examples were measured as follows, and the results are shown in Tables 3 and 4, respectively.

[0402]

[0403] (1) Melting index (MI) 2.16 ): Measured according to ASTM D1238 (Condition E, 190 ℃, 2.16 kg load).

[0404]

[0405] (2) Melting index (MI) 21.6 ): Measured according to ASTM D1238 (Condition E, 190 ℃, 21.6 kg load).

[0406]

[0407] (3) MFRR(MI 21.6 / MI 2.16 ): MI 21.6 (ASTM D1238, 190 ℃, 21.6 kg load) MI 2.16 (ASTM D1238, 190 ℃, 2.16 kg load) is the ratio divided by .

[0408]

[0409] (4) Density: Measured according to ASTM D1505 standard

[0410]

[0411] (5) Molecular weight

[0412] The weight-average molecular weight (Mw), number-average molecular weight (Mn), and Z-average molecular weight (Mz) were measured using gel permeation chromatography (GPC, manufactured by Waters).

[0413] Specifically, the measurement samples were evaluated using a Waters PL-GPC220 instrument using a Polymer Laboratories PLgel MIX-B 300 mm column. The evaluation temperature was 160℃, 1,2,4-trichlorobenzene was used as the solvent, and the flow rate was measured at a rate of 1 mL / min. The sample was prepared at a concentration of 10 mg / 10 mL and then supplied in an amount of 200 μL. The values ​​of Mw and Mn were measured using a calibration curve formed using polystyrene standards. The molecular weights (g / mol) of the polystyrene standards were 2,000 / 10,000 / 30,000 / 70,000 / 200,000 / 700,000 / 2,000,000 / 4,000,000 / 10,000,000, 9 types.

[0414]

[0415] (6) TREF and GPC analysis

[0416] Cross fraction chromatography (CFC) analysis was performed on the polyolefins of the above examples and comparative examples using the following method.

[0417] [Cross-fractionation chromatography analysis conditions (including TREF and GPC analysis)]

[0418] - Analysis equipment: Polymer Char CFC - 7890B (G3440D)

[0419] (Detector: Integrated Detector IR5 MCT)

[0420] - Sample preparation and loading: 32 mg of the polyolefin of the above examples or comparative examples was placed in a 10 mL vial and placed in an autosampler, 8 mL of 1,2,4-trichlorobenzene (TCB) was added, dissolved at 160°C for 90 minutes, and stabilized at 140°C for 20 minutes. After nitrogen purge, extraction was performed and loaded onto a temperature rising elution fractionation column (TREF column).

[0421] - Crystallization: The temperature of the sample previously loaded onto the TREF column was adjusted to 140℃, then cooled from 140℃ to 35℃ at a rate of 0.5℃ / min and maintained for 15 minutes.

[0422] The detailed conditions for the above stabilization and crystallization are as follows:

[0423]

[0424]

[0425] - Temperature Rising Elution Fractionation (TREF) Analysis: The previously crystallized sample was heated from 35°C to 120°C at a rate of 20°C / min to the following fraction temperature, then fixed, and the concentrations of the fractions eluted at that temperature for 5 minutes were measured. A TREF graph was derived from the concentration measurement results.

[0426] From the TREF graph, the content ratio of the soluble fraction (SF) eluted in the region of the elution temperature below 76°C based on the total weight of the entire elution fraction (W <76 ), the content ratio of the fraction eluted in the region of elution temperature 76℃ or higher and 88℃ or lower (W 76~88 ), the content ratio of the fraction eluted in the region where the elution temperature is 76℃ or higher (W ≥76 ), the content ratio of the fraction eluted in the region exceeding the elution temperature of 88℃ (W >88 ) were calculated respectively.

[0427] < fraction temperature>

[0428] 35℃ / 40℃ / 43℃ / 46℃ / 49℃ / 52℃ / 55℃ / 58℃ / 61℃ / 64℃ / 67℃ / 70℃ / 73℃ / 76℃ / 79℃ / 82℃ / 85℃ / 88℃ / 91℃ / 94℃ / 97℃ / 100℃ / 105℃ / 120℃

[0429]

[0430] In addition, TREF graphs obtained through the above analysis for the polyolefins of Examples 1 to 5 are shown in Figures 1 to 5, respectively.

[0431]

[0432] <Measurement conditions>

[0433]

[0434]

[0435] - GPC 분석: 앞서 TREF 분석에서 각 온도별 용출된 분획들을 CFC 장치 내 구비된 GPC 장치의 GPC Column으로 이동시킨 후, 하기 측정 조건에 따라 용출된 분자들의 분자량을 측정하였다.

[0436] Specifically, the weight average molecular weight (M) of the soluble fraction (SF) eluted in the region of the elution temperature below 76°C in the TREF graph <76 ), the weight average molecular weight (M) of the fraction eluted in the region of elution temperature 76℃ or higher and 88℃ or lower 76~88 ), the weight average molecular weight (M) of the fraction eluted in the region where the elution temperature is 76℃ or higher ≥76 ), the weight average molecular weight (M) of the fraction eluted in the region exceeding the elution temperature of 88℃ >88 ) were calculated respectively.

[0437] <Measurement conditions>

[0438]

[0439]

[0440] (7) Parameters T1, S1, P1

[0441] From the analysis results of (5) and (6) above, parameters T1, S1, and P1 were calculated using Equations 1 to 3 below, respectively.

[0442] [Formula 1]

[0443] T1 = 5*(W <76 * M <76 / 10 6 ) + (-1)*(W 76~88 * M 76~88 / 10 6 ) + (-2)*(W >88 * M >88 / 10 6 )

[0444] In the above equation 1,

[0445] W <76 , M <76The weight ratio (wt%) and weight average molecular weight (g / mol) of the polymer fraction eluted below 76℃, respectively.

[0446] W 76~88 , M 76~88 The weight ratio (wt%) and weight average molecular weight (g / mol) of the polymer fraction eluted at 76℃ or higher and 88℃ or lower, respectively.

[0447] W >88 , M >88 Each represents the weight ratio (wt%) and weight average molecular weight (g / mol) of the polymer fraction eluted in the region exceeding 88℃,

[0448] [Formula 2]

[0449] S1 = W >88 / W ≥76 + W ≥76 / 100

[0450] In the above equation 2,

[0451] W >88 The weight ratio (wt%) of the polymer fraction eluted in the region exceeding 88℃,

[0452] W ≥76 , M ≥76 Each represents the weight ratio (wt%) and weight average molecular weight (g / mol) of the polymer fraction eluted in the region above 76℃,

[0453] [Formula 3]

[0454] P1 = 1.2 * Mw / Mn + 0.4 * Mz / Mn

[0455] In the above equation 3,

[0456] Mw represents the weight average molecular weight (g / mol) of polyolefin, Mn represents the number average molecular weight (g / mol), and Mz represents the Z average molecular weight (g / mol).

[0457]

[0458] The results of the measurements for the polyolefins of the examples and comparative examples are shown in Tables 3 and 4, respectively.

[0459] Example 1 Example 2 Example 3 Example 4 Example 5MI 2.16 (g / 10 min)0.791.061.070.970.93MI 21.6 (g / 10min)36.2553.085048.1544.87MFRR45.8950.0846.7349.6448.25Density(g / cm 3 )0.92020.92440.92110.92530.9260W <76 (wt%)36.2938.6239.6332.3535.37M <76 (g / mol)285197235365255989277704220737W 76~88 (wt%)33.527.9528.2731.4127.89M 76~88 (g / mol)1649318403815423419540895359W ≥76 (wt%)63.7261.3960.3867.6364.64M ≥76 (g / mol)1174877580710333212578284039W >88 (wt%)30.2233.4432.1136.2236.75M >88 (g / mol)6489468927585176540275448Mn(g / mol)2350021800219002140022700 Mw(g / mol)113000113600107900108700111800Mz(g / mol)3359004853003256003 51100411200Mw / Mn4.815.214.935.084.93Mz / Mn14.2922.2614.8716.4118.11 T142.338.542.634.030.8S11.111.161.141.211.21P111.515.211.912.713.16

[0460] Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 MI 2.16 (g / 10 min)0.990.920.970.92MI 21.6 (g / 10 min)25.3022.6625.3522.17MFRR25.5624.6326.1324.1Density(g / cm 3 )0.92540.92500.92790.9173W<76 (wt%)24.1623.8621.4547.42M <76 (g / mol)215006218937146426185491W 76~88 (wt%)43.6743.3942.8935.5M 76~88 (g / mol)12069612620611710073331W ≥76 (wt%)75.8376.1578.5552.59M ≥76 (g / mol)10598011057410552868451W >88 (wt%)32.1632.7635.6617.09M >88 (g / mol)85997898699161058314Mn(g / mol)33700382003190030700Mw(g / mol)113400114800100700104500Mz(g / mol)2474002371 00220900240500Mw / Mn3.363.013.163.40Mz / Mn7.346.216.927.83T115.214.84.1539.4S11.181.191.240.85P17.06.16.567.22

[0461] Physical Property Evaluation of Polyolefin Films Films were manufactured using the polyolefins of the above examples and comparative examples, and their drop impact strength and modulus properties were evaluated. The results are shown in Table 5 below.

[0462]

[0463] (1) Film manufacturing

[0464] 1500 ppm of antioxidant (Songnox 1076 (Songwon): Songnox 1680 (Songwon) = 1:2 weight ratio) based on the total weight of polyolefin manufactured in the above examples or comparative examples was added and mixed, and extruded at an extrusion temperature of 190°C at an extrusion amount of 35 kg / hr using a twin screw extruder (TEK 30 MHS, manufactured by SMPLATECH CO., diameter 32 pi, L / D = 40), to manufacture a composition for forming a pellet-shaped film weighing about 18 mg.

[0465] The film-forming composition manufactured above was extruded under the following film extrusion conditions to manufacture a film.

[0466] In addition, the processing pressure (bar) applied to the single-extruder during film manufacturing was measured under the following film extrusion conditions.

[0467]

[0468] <Film extrusion conditions>

[0469] Single Screw Extruder (Eugene Engineering Single Screw Extruder, Blown Film M / C, 50 pi)

[0470] Melting temperature (or extrusion temperature): 170℃

[0471] Die Gap 2.0mm

[0472] Die diameter: 120mm

[0473] Blown-Up Ratio: 2.5

[0474] Maintain Frost Line Height at 250~260mm

[0475] Sample extrusion rate: 300~500g / min

[0476] Film thickness: 50㎛

[0477]

[0478] (2) Dart drop impact strength (gf)

[0479] The drop impact strength of the 50㎛ thick film manufactured above was measured according to ASTM D1709 [Method A], and the average value was taken by measuring more than 20 times per film sample.

[0480]

[0481] (3) 1% MD and TD secant modulus (kgf / cm) 2 )

[0482] For the 50㎛ thick film manufactured above, the slope was measured by drawing a straight line along the stress-strain curve from the origin to 1% strain when pulled in the machine direction (MD) and the transverse direction (TD) according to ASTM D882 using an Instron UTM (Universal Testing Machine).

[0483]

[0484] Drop impact strength (gf) 1% MD modulus (kgf / cm) 2 )1% TD modulus(kgf / cm 2 ) Pneumatic pressure (bar) Example 1200022672884185 Example 2127628193860180 Example 3189225253367185 Example 4110028773910180 Example 5105432614776182 Comparative example 145329773499240 Comparative example 250229363605240 Comparative example 328231194000240 Comparative example 4200016841965210

[0485] Referring to Table 5, in the case of embodiments in which the T1 and S1 parameters satisfy a predetermined range according to one embodiment of the present invention, excellent drop impact strength of 1100 gf or more and 2000 kgf / cm 2 It shows an MD and TD secant elastic modulus of 1% or more, and it can be confirmed that the processability is excellent when the film is extruded at a processing pressure of 200 bar or less.

Claims

1. Polyolefin satisfying the conditions (1) to (3) below: (1) Density measured by ASTM D1505 of 0.920 to 0.930 g / cm 3 ; (2) In the temperature rising elution fractionation (TREF) graph during cross fraction chromatography (CFC) analysis, the toughness parameter (T1) expressed by Equation 1 satisfies T1>25; [Formula 1] T1 = 5*(W <76 * M <76 / 10 6 ) + (-1)*(W 76~88 * M 76~88 / 10 6 ) + (-2)*(W >88 * M >88 / 10 6 ) In the above equation 1, W <76 , M <76 The weight ratio (wt%) and weight average molecular weight (g / mol) of the polymer fraction eluted below 76℃, respectively. W 76~88 , M 76~88 The weight ratio (wt%) and weight average molecular weight (g / mol) of the polymer fraction eluted at 76℃ or higher and 88℃ or lower, respectively. W >88 , M >88 Each represents the weight ratio (wt%) and weight average molecular weight (g / mol) of the polymer fraction eluted in the region exceeding 88℃, (3) In the temperature rise elution fractionation (TREF) graph during cross-fraction chromatography (CFC) analysis, the Stiffness parameter (S1) expressed by Equation 2 satisfies S1>1.1; [Formula 2] S1 = W >88 / IN ≥76 + In ≥76 / 100 In the above equation 2, W >88 The weight ratio (wt%) of the polymer fraction eluted in the region exceeding 88℃, W ≥76 , M ≥76 Each represents the weight ratio (wt%) and weight average molecular weight (g / mol) of the polymer fraction eluted in the region above 76℃.

2. In paragraph 1, Polyolefins whose processing parameter (P1) expressed by Equation 3 satisfies P1>11 in the graph measured through cross-fraction chromatography (CFC): [Formula 3] P1 = 1.2 * Mw / Mn + 0.4 * Mz / Mn In the above equation 3, Mw refers to the weight average molecular weight (g / mol) of polyolefin, Mn refers to the number average molecular weight (g / mol), and Mz refers to the Z average molecular weight (g / mol).

3. In paragraph 1, Melt index MI measured by ASTM D1238 2.16 Polyolefin satisfying this 0.5 to 2 g / 10 min.

4. In paragraph 1, MFRR (MI) measured by ASTM D1238 21.6 / MI 2.16 ) polyolefin satisfying 35 to 60.

5. In paragraph 1, A polyolefin satisfying a molecular weight distribution (Mw / Mn) of 4.5 to 6.

6. In paragraph 1, The above polyolefin is a polyolefin that is a copolymer of ethylene and olefin monomers.

7. In paragraph 6, The above olefin monomer is propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, or 1-eicosene, polyolefin.

8. A film comprising a polyolefin according to paragraph 1.

9. In paragraph 8, The film has a drop impact strength of 900 gf or more, measured according to Method A of ASTM D 1709 under the conditions of BUR 2.3 to 3 and a film thickness of 50 to 65 ㎛.

10. In paragraph 8, The film has a 1% MD and TD secant modulus of 2000 kgf / cm2, respectively, measured according to ASTM D882 under conditions of BUR 2.3 to 3 and a film thickness of 50 to 65 ㎛. 2 Strange, film.

Images